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WO1997020846A1 - Porphyrines substituees - Google Patents

Porphyrines substituees Download PDF

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Publication number
WO1997020846A1
WO1997020846A1 PCT/GB1996/002899 GB9602899W WO9720846A1 WO 1997020846 A1 WO1997020846 A1 WO 1997020846A1 GB 9602899 W GB9602899 W GB 9602899W WO 9720846 A1 WO9720846 A1 WO 9720846A1
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Prior art keywords
optionally substituted
alkyl
compound
halogen
alkoxy
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PCT/GB1996/002899
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English (en)
Inventor
Lionel Robert Milgrom
Gokhan Yahioglu
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Brunel University
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Priority to AU76348/96A priority Critical patent/AU7634896A/en
Publication of WO1997020846A1 publication Critical patent/WO1997020846A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
    • A61K41/0057—Photodynamic therapy with a photosensitizer, i.e. agent able to produce reactive oxygen species upon exposure to light or radiation, e.g. UV or visible light; photocleavage of nucleic acids with an agent
    • A61K41/0071—PDT with porphyrins having exactly 20 ring atoms, i.e. based on the non-expanded tetrapyrrolic ring system, e.g. bacteriochlorin, chlorin-e6, or phthalocyanines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
    • C09K19/3488—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring having more than 6 members, e.g. macrocycles, phthalocyanines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/40—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen or sulfur, e.g. silicon, metals

Definitions

  • Porphyrin is given by the following general formula:
  • Porphyrins have found uses in numerous applications including precursors for novel conducting polymers (Wagner et al, J. Am. Chem. Soc, 1994, 116, 9759; Anderson, Inorg. Chem., 1994, 33, 972 and Arnold et al, Tetrahedron, 1992, 48, 8781); non- linear optically active (NLO) materials (Anderson et al, Angew. Chem. Int. Ed. Engl., 1994, 33, 655 and Arnold et al, J. Am. Chem. Soc, 1993, 115, 12197); photosynthetic m ⁇ del compounds (Wagner et al, J. Org. Chem., 1995, 60, 5266.
  • NLO non- linear optically active
  • R 1 , R 2 , R 3 and R 4 are each independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally subsituted alkenyl, optionally subsituted alkenyloxy, Si(alkyl) 3 , halogen, CHO, OH, CN, NO 2 , NO, NR 5 R 6 or the following Formula II:
  • R 5 and R 6 are each independently hydrogen, optionally subsituted alkyl, optionally substituted alkenyl, optionally substituted aryl, halogen or hydroxy;
  • X, Y, X 1 , Y 2 and Z are each independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally subsituted alkenyl, optionally subsituted alkenyloxy, Si(alkyl) 3 , halogen, CHO, OH, CN, NO 2 , NO, NR 5 R 6 , any adjacent two groups taken together form a -(OCH 2 CH 2 ) n - group wherein n is 1 , 2 or 3, or the following Formula III: wherein J is a single bond, ⁇ , CH 2 O, OCH 2 , COO, OOC, NHCO, CONH, CH 2 or O;
  • Q is H, optionally substituted alkyl, optionally substituted alkoxy, optionally subsituted alkenyl, optionally subsituted alkenyloxy, Si(alkyl) 3 , halogen, CHO, OH, CN, NO 2 , NO, NR 5 R 6 ; is optionally substituted aryl or optionally subsituted heteroaryl;
  • R 1 , R 2 , R 3 or R 4 is selected from Formula II;
  • M is 2H with each of the two nitrogen atoms indicated being bonded to a single hydrogen, or M is a metal atom, metal compound or silicon or a compound of silicon.
  • the metal atom may be present for example as the metal with an oxidation state of +2 or it may be present with other ligands (or anions) attached to it. These ligands (anions) may serve the purpose of altering the hydrophobicity of the molecule as a whole.
  • suitable anions include bromine, chlorine or oxide.
  • suitable metals include Ni, Pb, V, Pd, Co, Nb, Al, Sn, Zn, Cu, Mg, Ca, In, Ga, Fe, Eu, Lu, Pt, Ru, Mn and Ge.
  • Compounds of general Formula I may also be protonated so that they carry a +1 or +2 charge.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Z, X 1 , Y 2 , X, Y or Q is alkyl, or contains an alkyl moiety, it can be straight or branched chain and is preferably C 1-20 alkyl.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are more preferably C 1-6 alkyl, even more preferably C 1-4 alkyl, for example methyl, ethyl, propyl, iso-propyl, n-butyl, isobutyl, sec-butyl or t-butyl.
  • Z, X 1 , Y 2 , X, Y or Q are more preferably C 7-20 alkyl for example, -C 7 H 15 -, -C 8 H 17 , -C 9 H 19 , -C 10 H 21 , -C 11 H 23 , -C 12 H 25 , -C 13 H 27 .
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Z, X 1 , Y 2 , X, Y or Q may comprise one or more
  • substitutents chosen from halogen, NO 2 , CN, -COOR 5 or a salt thereof, hydroxy or alkoxy.
  • R 1 , R 2 , R 3 , R 4 , Z, X 1 , Y 2 , X, Y or Q is a subsituted alkenyl group, or contains an alkenyl moiety, it may be straight or branched chain and is preferably C 2-20 alkenyl.
  • R 1 to R 6 are more preferably C 2-6 , even more preferably C 2-4 alkenyl, for example vinyl, but-3-enyl or 3-methyl-but-3-enyl.
  • Z, X 1 , Y 2 , X, Y or Q are more preferably C 7-20 alkenyl.
  • R 1 , R 2 , R 3 , R 4 , Z, X 1 , Y 2 , X, Y or Q is a subsituted alkenyl group, or contains a substituted alkenyl moiety, it may comprise one or more substituents chosen from halogen, -COOR 5 or a salt thereof, hydroxy, NO 2 and CN.
  • R 1 , R 2 , R 3 , R 4 , Z, X 1 , Y 2 , X, Y or Q is an optionally subsituted alkoxy or alkenyloxy group, or contains a subsituted alkoxy or alkenyloxy moiety, it may be straight or branched chain and is preferably C 1-20 alkoxy or alkenyloxy.
  • R, to R 6 are more preferably C 1-6 alkoxy or alkenyloxy.
  • Z, X, Y, X 1 , Y 2 or Q are more preferably C 7-20 alkoxy alkenyloxy.
  • R 1 , R 2 , R 3 , R 4 , Z, X 1 , Y 2 , X, Y or Q is the group COOR 5 , it is preferably COOH; an alkoxycarbonyl group, for example methoxycarbonyl and ethoxycarbonyl; or a haloalkenyloxycarbonyl group, for example 3,4,4-trifluorobut-3-enyloxycarbonyl, 3-methyl-4,4-difluorobut-3-enyloxycarbonyl.
  • a or B is aryl, or contains an aryl moiety, it is preferably C 6-10 aryl, more preferably it is phenyl.
  • a or B is heteroaryl, or contains a heteroaryl moiety, it is preferably a 5 or 6 membered ring contaiing at least O, N or S atom as the heteroatom, for example pyridine, pyrrole, pyrazine, imidazole, furan or thiophene.
  • a or B is subsituted aryl or heteroaryl it may comprise one or more substituents chosen from alkyl, alkoxy, haloalkyl, halogen, COOR 5 or a salt thereof, CN or NO 2 .
  • Examples of these groups are 4-methylphenyl, 4-chIorophenyl, 4- fluorophenyl, 4-nitrophenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl, 4- chlorobenzyl, 4-fluorobenzyl, 3-trifluoromethylbenzyl, 4-trifluoromethylbenzyl, 4- nitrobenzyl and 4-methylbenzyl.
  • R 1 , R 2 , R 3 , R,, R 5 , R 6 , Z, X 1 , Y 2 , X, Y or Q is halogen, or contains a halogen moiety, it is preferably fluorine, chlorine, bromine or iodine. Even more preferably, it is fluorine, chlorine or bromine.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Z, X 1 , Y 2 , X, Y or Q is a haloalkyl or haloalkenyl group it may contain one or more halogen atoms, preferably chlorine, fluorine or bromine.
  • Examples of these groups are fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoroethyl, 3,3-dichloroprop-2-enyl, 2-chloroprop-2-enyl, 3,4,4-trifluorobut-3-enyl, 4-fluorobut-3-enyl, 4,4-difluorobut-3-enyl and 3-methyl-4,4-difluorobut-3-enyl.
  • any one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Z, X 1 , Y 2 , X, Y or Q is a haloalkoxy group it may contain one or more halogen atoms, preferably chlorine, fluorine or bromine.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Z, X 1 , Y 2 , X, Y or Q is -NR 5 R 6 it is preferably NH 2 ; a mono-alkylamino group, for example methylamino or ethylamino; or a di-alkylamino group, for example dimethylamino or diemylamino.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Z, X 1 , Y 2 , X, Y or Q is Si(alkyl) 3 it is preferably Si(C 1-6 alkyl), for example trimethylsilyl, triethylsilyl or triisopropylsilyl.
  • R 1 , R 2 , R 3 , and R 4 are all a group of Formula II.
  • R 1 and R 3 are a group of Formula II and R 2 and R 4 are H or Si(CH 3 ) 3 , or R 2 and R 4 are a group of Formula II and R 1 and R 3 are H or Si(CH 3 ) 3 .
  • M is 2H or Zn.
  • M is a silicon compound it is Si-alkoxy or Si-OH.
  • any one of X, Z or Y is C 1-20 alkyl or alkoxy.
  • X and Z or Y and Z together form a - (OCH 2 CH 2 ) n - group.
  • Porphyrins usually have a characteristic red colour due to an intense absorption (called the B band: a pi-pi* transition) in the region 400-420nm.
  • the B band a pi-pi* transition
  • Q bands weaker absorptions
  • M 2H, 4 bands
  • M 4H, 2 bands
  • M M, 2 bands
  • the compounds of the present invention may be used in a broad range of applications including those applications mentioned in the introduction of this application.
  • Other uses include pigments or dyes, as components of discotic liquid crystal phases (in particular they may also be used a precursors for discotic liquid crystals), two dimensional conjugated polymeric arrays, see Drain and Lehn, J. Chem. Soc, Chem. Commun., 1994, 2313: as reverse saturable absorbers and as agents for photodynamic therapy.
  • the types of liquid crystal devices include linear and non-linear electrical, optical and electro-optical devices, magneto-optical devices and devices providing responses to stimuli such as temperature changes and total or partial pressure changes.
  • the compounds of the present invention may also be used in biaxial nematic devices and as second or third order non-linear optic (NLO) materials.
  • NLO non-linear optic
  • Z' is an electron donating group such as alkyl, alkoxy, for example C 1-15 , dialkylamine or diarylamine and Z" is an electron withdrawing group such as NO 2 , CN, halogen, NO, NH 2 , an ester or carboxylic acid may be useful as biaxial nematic liquid crystal materials possessing NLO properties.
  • Z" is an electron withdrawing group and Z' is an electron donating group, then the materials below may be of use as second and/or third order NLO materials.
  • Ga x Al 1-x As lasers where x is from 0 to 1, and is preferably 1, has proven popular in the above applications because they can provide laser energy at a range of
  • Gallium arsenide lasers provide laser light at wavelengths of about 850nm, and are useful for the above applications. With increasing Al content (x ⁇ 1), the laser wavelength may be reduced down to about 750nm. The storage density an be increased by using a laser of shorter wavelength.
  • the compounds of the present invention may be suitable as optical storage media and may be combined with dyes for use in laser addressed systems, for example in optical recording media.
  • the porphyrin will absorb in the near-infrared.
  • the near-infrared absorber may be coated or vacuum-deposited onto a transparent substrate.
  • EP 0 337 209 A2 describes the processes by which the above optical-recording media may be made.
  • the compounds of the present invention are useful in near- infrared absorption filters and liquid crystal display devices. As described similarly in EP 0
  • display materials can be made by mixing a near-infrared absorber of Formula I with liquid crystal materials such as nematic liquid crystals, smectic liquid crystals and cholesteric liquid crystals.
  • liquid crystal materials such as nematic liquid crystals, smectic liquid crystals and cholesteric liquid crystals.
  • the compounds of the present invention may be incorporated into liquid crystal panels wherein the near infrared-absorber is incorporated with the liquid crystal and a laser beam is used to write an image.
  • Another preferred compound is 10,20-mesobis(arylethynyl)porphyrin as a calamitic mesogen.
  • Langmuir Blodgett films incorporating porphyrins of the present invention may be laid down using conventional and well known techniques, see R.H. Tredgold in "Order in Thin Organic Films", Cambridge University Press, p74, 1994 and reference therein.
  • Polymerised porphyrins may also be used in, for example, Langmuir Blodgett films.
  • the porphyrin may be incorporated into a polymer.
  • Polymerisation may be effected by one or more of the positions R 1 -R 4 in Formula I for example via one or more of the OH groups or via the central metal atom or metal compound or polymerisation may be achieved by a combination of the above techniques.
  • An example of a suitable substituent which may be used to effect polymerisation is an unsaturated substituent such as an alkene group.
  • An example of a repeating unit of one such polymer is shown below:
  • Main chain or side chain liquid crystal polymers may also be made using the compounds of the present invention or metal-metal linked liquid crystal polymers.
  • We have synthesised unsymmetrical chlorphyrins, i.e. , with one type of arylethynyl moiety in the 5- and 15-meso-positions and a different arylethynyl moiety in the 10- and 20-positions. Examples are shown below (where Z'" alkyl):
  • porphyrins with two bare acetylenes. These can be polymerised or copolymerised (e.g.. with poly(phenylene vinylene)) to make electroluminescent polymers. Alternatively, the bare acetylenic substituents may be reacted individually with electron donor and acceptor groups to furnish "push-pull" acetylenic porphyrins with large 1st-order hyperpolarisabilities.
  • protecting groups e.g. Me 3 Si-
  • Langmuir Blodgett Films incorporating compounds of the present invention may be used as optical or thermally addressable storage media.
  • the compounds of the present invention may also be used as molecular wires, see R.J.M. Nolte at al, Angew. Chem. Int. Ed. Eng., 1994, 33(21), 2173.
  • Water soluble paramagnetic manganese complexes of the porphyrins of the present invention may be used in methods for enhancing images obtained from magnetic resonance imaging of a region of regions containing a malignant tumour growth.
  • the compounds of the present invention may be used as photodynamic therapeutic (PDT) agents.
  • PDT photodynamic therapeutic
  • the combination of a sensitiser and electromagnetic radiation for the treatment of cancer is commonly known as photodynamic therapy.
  • dye compounds are administered to a tumour-bearing subject, these dye substances may be taken up, to a certain extent by the tumour.
  • an appropriate light source e.g. a laser
  • the tumour tissue is destroyed via the dye mediated photo-generation of a species such as singlet oxygen or other cytotoxic species such as free radicals, for example hydroxy or superoxide.
  • a species such as singlet oxygen or other cytotoxic species such as free radicals, for example hydroxy or superoxide.
  • Porphyrins absorb strongly in the blue, which means they are not well “tuned” to work with red light and so their PDT effect is not very penetrating.
  • macrocycles with intense, longer- wave absorptions e.g., chlorins, phthalocyanines,
  • Chlorphyrins have better red-light absorbing properties than porphyrins, and would be well-suited for PDT. Further, chlorphyrins showing excellent triplet-state yields and lifetimes.
  • PCT/GB94/01847 describes substituted metallophthalocyanines and phthalocyanines as PDT agents. Many of the techniques described therein (and references cited) are applicable to the current materials.
  • Metalloporphyrins particularly the Pt and Pd complexes, have been used in phosphoimmunoassays (PLA) [AP Savitsby et al, Dokl. Acad. Nauk SSSR, 1989, 304, 1005]. Also the extreme sensitivity of these metalloporphyrins' triplet excited states to dissolved oxygen has been used to measure dissolved O 2 levels in biological systems [TJ Green et al, Anal. Biochem. , 1988, 174, 73; EP 0 127 797A and US-A- 4,707,454]. Because porphyrins subsituted with four mw ⁇ arylethynyl groups have very high triplet yields, we envisage they will have improved characteristics of PLA and/or sensitivity to dissolved O 2 .
  • the compound of Formula contains at least one crown-ether.
  • a preferred example is shown below:
  • chlorphyrins with aryl crown-ether substituents will complex suitable metal cations. This will be efficiently 'communicated' to the macrocycle, via the acetylenic groups. Such a substituted chlorphyrin will experience significant alteration of the absorption and/or emission properties.
  • NLO-active unsymmetrical chlorphyrins with two crown-ether substituents may change their NLO properties on metal complexation.
  • crown-ether-substituted chlorphyrins could act as sensors for low concentrations of metals.
  • Figure 6 illustrates a liquid crystal device in which the materials of the current invention may be incorporated.
  • Reagents and conditions used in the synthetic routes of Figures 1 and 2 are as follows: i) BuLi/THF/-78°C
  • Reagents and conditions used in the synthetic route of Figure 4 are as follows:
  • Butyllithium was ordered as a 1.6 molar solution in THF from Aldrich Chemical Co.
  • K 2 CO 3 anhydrous potassium carbonate
  • 4-Octylphenylpropynal 3 was prepared from 4-octylphenylactetylene by quenching the acetylide (formed by low temperature reaction with BuLi. see Brandsma in "Preparative Acetylene Chemistry” 2nd Edition, Studies in Organic Chemistry 34, Elsevier Science Publishers (Amsterdam), 1998, Chapter 2, pl3) with DMF, followed by acid hydrolysis.
  • 4-Nonyloxyphenylpropanal 5 was prepared in a three-step synthesis from 4- hydroxybenzaidehyde. Alkylation of the phenolic -OH with 1 -bromononane was followed by a Corey and Fuchs reaction with CBr 4 , triphenylphosphine and zinc (see Tetrahedron Lett.. 1972, 3769) to give ⁇ , ⁇ -dibromostyryl derivative 4. Low temperature reaction of 4 with 2.5 equivalents of BuLi followed by quenching of the acetylide with DMF and acid hydrolysis yielded 5 Care was taken not to allow the acidity of this reaction to drop below pH 6-7 otherwise no arylpropynal was produced
  • porphyrin 2c in 3% yield.
  • a second porphyrin- like product was separated as the major product via column chromatography on silica gel, eluting with DCM.
  • Alkynyl meso substituents significantly red-shift the porphyrin B and Q bands (see Anderson, Tetrahedron Lett., 1992, 33, 1 101). Thus, compared to
  • the B band of porphyrin 1 (shown below) is red-shifted by about 34nm. Replacing the trimethylsilyl group of 1 with an aryl group increases the B and Q band red shifts even further (46 ⁇ 2a ⁇ , 54 ⁇ 2b ⁇ , and 57 ⁇ 2c ⁇ nm for the B band). In addition, there is a marked increase in the main Q band absorption relative to that of the B band, and two of the Q bands appear as smaller shoulders either side of the main Q band absorption.
  • porphyrin-like by-products may be isomers of 2b and 2c - containing 2-aza-21 -carbaporphyrin macrocycle as described by Chmielewskj at al, Chem. Eur. J., 1995, 1, 68.
  • trans-disubstituted meso-tetraethynylporphyrins in accordance with the present invention may be prepared by coupling acetylenic dipyrromethanes with substituted propynals.
  • the synthesis involves reaction of arylethynyl dipyrromethanes with a variety of propynals.
  • arylethynyl dipyrromethanes were prepared in high yield via Lindsey' s procedure.
  • Chlorphyrins were synthesised by condensation of propynals prepared using literature methods with arylethynyl dipyrromethanes at -25oC in the presence of BF 3 .OEt 2 as catalyst. DDQ oxidation of the resulting porphyrinogens gave high yields of chlorphyrins.
  • a preferred variation on this process involves protection of the acteylene moiety in the acetylene-aldehyde precursor with dicobaltoctacarbonyl. Following the preparation of the porphyrin. either by one-pot Lindsey synthesis or via the dipyrromethane, the protecting group is photochemically removed to afford the mejotetraarylethynylporphyrin in much improved yield.
  • A is phenyl are given below in Tables I and II; although A could just as easily be for example pyridine, pyrrole, pyrazine, imidazole, furan or thiophene.
  • the Liquid crystal device consists of two transparent plates, 1 and 2, for example made from glass. These plates are coated on their internal face with transparent conducting electrodes 3 and 4. An alignment layer is introduced onto the internal faces of the cell so that a planar orientation of the molecules making up the liquid crystalline material will be approximately parallel to the glass plates 1 and 2. This is done by coating the glass plates 1,2 complete with conducting electrodes 3,4 with layers of film 5 and 6 of a suitable polymer, e.g. polyimide.
  • the electrodes 3,4 may be formed into row and column electrodes so that the intersections between each column and row form an x,y matrix of addressable elements or pixels.
  • the films 5,6 Prior to the construction of the cell the films 5,6 are rubbed with a roller covered in cloth (for example made from velvet) in a given direction, the rubbing directions being arranged parallel (same or opposite direction) upon construction of the cell.
  • Liquid crystal material 8 is introduced between glass plates 1,2 by filling the space in between them. This may be done by flow filling the cell using the standard techniques.
  • the spacer 7 is sealed with an adhesive 9 in a vacuum using an existing technique.
  • Polarisers 10, 11 may be arranged in front of and behind the cell.
  • Alignment layers may be introduced onto one or more cell walls by one or more of the standard surface treatment techniques such as rubbing, oblique evaporation or as described above by the use of polymer aligning layers.
  • the device may operate in a transmissive or reflective mode.
  • a transmissive or reflective mode In the former, light passing through the device, e.g. from a tungsten bulb, is selectively transmitted or blocked to form the desired display.
  • a mirror, or diffuse reflector 12 In the reflective mode a mirror, or diffuse reflector 12 is placed behind the second polariser 11 to reflect ambient light back through the cell and two polarisers. By making the mirror partly reflecting the device may be operated both in a transmissive and reflective mode.
  • a single polariser and dye material may be combined.

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Abstract

L'invention se rapporte à un composé de la formule générale (I) dans laquelle R1, R2, R3 et R4 représentent chacun, indépendamment, H, alkyle éventuellement substitué, alcoxy éventuellement substitué, alcényle éventuellement substitué, alcényloxy éventuellement substitué, Si(alkyl)3, halogène, CHO, COOR5, OH, CN, NO2, NO, NR5R6 ou la formule (II) dans laquelle (A) représente aryle éventuellement substitué ou hétéroaryle éventuellement substitué; R5 et R6 représentent chacun, indépendamment, hydrogène, alkyle éventuellement substitué, alcényle éventuellement substitué, aryle éventuellement substitué, halogène ou hydroxy; X, Y, X1, Y2 et Z représentent chacun, indépendamment, H, alkyle éventuellement substitué, alcoxy éventuellement substitué, alcényle éventuellement substitué, alcényloxy éventuellement substitué, Si(alkyl)3, halogène, CHO, COOR5, OH, CN, NO2, NO, NR5R6, n'importe lequel des deux groupes adjacents réunis formant un groupe a-(OCH2CH2)n dans lequel n vaut 1, 2 ou 3, ou la formule (III) dans laquelle J représente une liaison unique, , CH2O, OCH2, COO, OOC, NHCO, CONH, CH2 ou O; Q représente H, alkyle éventuellement substitué, alcoxy éventuellement substitué, alcényle éventuellement substitué, alcényloxy éventuellement substitué, Si(alkyl)3, halogène, CHO, COOR5, OH, CN, NO2, NO. NR5R6; (B) représente aryle éventuellement substitué ou hétéroaryle éventuellement substitué; à condition que au moins un de R1, R2, R3 ou R4 soit sélectionné à partir de la formule (II); M représente 2H, chacun des deux atomes d'azote indiqués étant liés à un seul hydrogène, ou M représente un atome métallique, un composé métallique ou un silicium ou un composé de silicium. L'invention se rapporte également aux utilisations de ce composé, notamment dans un dispositif à cristaux liquides, comme absorbeur saturable inverse, agent thérapeutique photodynamique, et dans un dispositif nématique biaxial.
PCT/GB1996/002899 1995-11-23 1996-11-22 Porphyrines substituees WO1997020846A1 (fr)

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WO1999050269A3 (fr) * 1998-03-31 1999-11-18 Schastak Astrid Nouvelles porphyrines et leur utilisation
EP1063236A1 (fr) * 1999-06-07 2000-12-27 Agency of Industrial Science and Technology of Ministry of International Trade and Industry Complexes de silicium photoconducteurs, matériaux de cristaux liquides, compositions les contenant et éléments les utilisant
US6630128B1 (en) 1998-08-28 2003-10-07 Destiny Pharma Limited Porphyrin derivatives their use in photodynamic therapy and medical devices containing them
WO2004046151A2 (fr) * 2002-11-21 2004-06-03 Photobiotics Limited Derives de porphyrine
WO2004076461A1 (fr) * 2003-02-26 2004-09-10 Photobiotics Limited Derives de porphyrine
US6869479B2 (en) * 2002-03-29 2005-03-22 Altair Center, Llc Method of laser-assisted fabrication of optoelectronic and photonic components
WO2005000854A3 (fr) * 2003-06-06 2005-05-12 Eukarion Inc Metalloporphyrines de faible poids moleculaire biodisponibles par voie orale
US6906050B2 (en) 2001-05-31 2005-06-14 Miravant Pharmaceuticals, Inc. Substituted porphyrin and azaporphyrin derivatives and their use in photodynamic therapy, radioimaging and MRI diagnosis
US6953570B2 (en) 2001-08-22 2005-10-11 Montana State University Porphyrins with enhanced multi-photon absorption cross-sections for photodynamic therapy
WO2007081505A2 (fr) * 2006-01-04 2007-07-19 Kent State University Porphyrines a cristaux liquides discotiques a echelle nanometrique
WO2007081490A1 (fr) * 2006-01-04 2007-07-19 Kent State University Porphyrines à cristaux liquides discotiques et complexes metalliques collecteurs de lumière
CN102408745A (zh) * 2011-11-25 2012-04-11 北京科技大学 一类以四苯基卟啉为核心的不对称染料分子及其制备方法

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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6410568B1 (en) 1998-03-31 2002-06-25 Astrid Schastak Porphyrins and their use as photosensitizer
WO1999050269A3 (fr) * 1998-03-31 1999-11-18 Schastak Astrid Nouvelles porphyrines et leur utilisation
US6630128B1 (en) 1998-08-28 2003-10-07 Destiny Pharma Limited Porphyrin derivatives their use in photodynamic therapy and medical devices containing them
EP1063236A1 (fr) * 1999-06-07 2000-12-27 Agency of Industrial Science and Technology of Ministry of International Trade and Industry Complexes de silicium photoconducteurs, matériaux de cristaux liquides, compositions les contenant et éléments les utilisant
US6906050B2 (en) 2001-05-31 2005-06-14 Miravant Pharmaceuticals, Inc. Substituted porphyrin and azaporphyrin derivatives and their use in photodynamic therapy, radioimaging and MRI diagnosis
US6953570B2 (en) 2001-08-22 2005-10-11 Montana State University Porphyrins with enhanced multi-photon absorption cross-sections for photodynamic therapy
US6869479B2 (en) * 2002-03-29 2005-03-22 Altair Center, Llc Method of laser-assisted fabrication of optoelectronic and photonic components
WO2004046151A2 (fr) * 2002-11-21 2004-06-03 Photobiotics Limited Derives de porphyrine
WO2004046151A3 (fr) * 2002-11-21 2004-08-12 Photobiotics Ltd Derives de porphyrine
WO2004076461A1 (fr) * 2003-02-26 2004-09-10 Photobiotics Limited Derives de porphyrine
WO2005000854A3 (fr) * 2003-06-06 2005-05-12 Eukarion Inc Metalloporphyrines de faible poids moleculaire biodisponibles par voie orale
US7649091B2 (en) 2003-06-06 2010-01-19 Eukarion, Inc. Orally bioavailable low molecular weight metalloporphyrins as antioxidants
WO2007081505A2 (fr) * 2006-01-04 2007-07-19 Kent State University Porphyrines a cristaux liquides discotiques a echelle nanometrique
WO2007081490A1 (fr) * 2006-01-04 2007-07-19 Kent State University Porphyrines à cristaux liquides discotiques et complexes metalliques collecteurs de lumière
WO2007081505A3 (fr) * 2006-01-04 2007-08-30 Univ Kent State Ohio Porphyrines a cristaux liquides discotiques a echelle nanometrique
US7279570B2 (en) 2006-01-04 2007-10-09 Kent State University Nanoscale discotic liquid crystalline porphyrins
US7291727B1 (en) 2006-01-04 2007-11-06 Kent State University Light-harvesting discotic liquid crystalline porphyrins and metal complexes
CN102408745A (zh) * 2011-11-25 2012-04-11 北京科技大学 一类以四苯基卟啉为核心的不对称染料分子及其制备方法
CN102408745B (zh) * 2011-11-25 2014-06-18 北京科技大学 一类以四苯基卟啉为核心的不对称染料分子及其制备方法

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GB9524028D0 (en) 1996-01-24
AU7634896A (en) 1997-06-27

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